Phenylazo- or naphthylazobenzenes having thioether groups

ABSTRACT

Reactive dyes of the formula I   &lt;IMAGE&gt;   &lt;IMAGE&gt;  where n is 0 or 1 R1, R2 and R3 are in each case hydrogen, C1-C4-alkyl or phenyl, R4 is fluorine, chlorine, bromine, C1-C4-alkylsulfonyl, phenylsulfonyl or a radical of the formula   &lt;IMAGE&gt;  L is a bridge member, A is unsubstituted or substituted C2-C8-alkylene, Y is vinyl or a radical of the formula -CH2-CH2-Q, Q being a group which can be removed under alkaline reaction conditions, and D is phenyl or naphthyl, it being possible for these radicals to be substituted, and a process for preparing reactive dyes by oxidation of the abovementioned compounds are described.

This is a Division of application Ser. No. 08/254,764, filed on Jun. 6,1994.

The present invention relates to novel compounds of the formula I##STR3## where n is 0 or 1

R¹, R² and R³ are identical or different and independently of oneanother are in each case hydrogen, C₁ -C₄ -alkyl or phenyl,

R⁴ is fluorine, chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonylor a radical of the formula ##STR4## L is a bridge member, A is C₂ -C₈-alkylene which may be interrupted by 1 to 3 ether oxygen atoms, iminogroups or C₁ -C₄ -alkylimino groups,

Y is vinyl or a radical of the formula --CH₂ --CH₂ --Q, Q being a groupwhich can be removed under alkaline reaction conditions, and

D is phenyl or naphthyl, it being possible for these radicals to bemono- or polysubstituted by hydroxysulfonyl, carboxyl, C₁ -C₄-alkoxycarbonyl, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro orvinylsulfonyl,

and a process for preparing reactive dyes by oxidation of theabovementioned compounds.

EP-A-520,241 describes the preparation of azo reactive dyes, startingfrom azo compounds which contain a 2-hydroxyethylthioether group,converting this into the 2-hydroxyethylsulfonyl group and thengenerating a sulfuric acid monoester group therefrom.

U.S. Pat. No. 5,182,371 discloses reactive dyes which are based on themolecular structure of the abovementioned compounds of the formula I,but which contain a sulfonyl group instead of the thioether group. Thesedyes have particularly favourable application properties, in particularhigh lightfastness, high tinctorial strength and good fixing behavior.

It is an object of the present invention to provide novel intermediateswhich are advantageously suitable for preparing these reactive dyes.

We have found that this object is achieved by the compounds of theformula I described in greater detail at the beginning.

In the present case, the novel compounds of the formula I are as a ruleindicated in the form of a free acid. Of course, however, their saltsare also additionally included.

Suitable salts in this case are metal or ammonium salts. Metal salts arein particular the lithium, sodium or potassium salts. Ammonium salts forthe purpose of the invention are to be understood as meaning those saltswhich contain either unsubstituted or substituted ammonium cations.Substituted ammonium cations are e.g. monoalkyl-, dialkyl-, trialkyl-,tetraalkyl- or benzyltrialkylammoniumcations or those cations which arederived from nitrogen-containing 5- or 6-membered saturatedheterocycles, such as pyrrolidinium, piperidinium, morpholinium,piperazinium or N-alkylpiperazinium cations or their N-monoalkyl- orN,N-dialkyl-substituted products. Alkyl is in this case in general to beunderstood as meaning straight-chain or branched C₁ -C₂₀ -alkyl whichcan be substituted by hydroxyl groups and/or interrupted by ether oxygenatoms.

If substituted phenyl radicals occur in the abovementioned formula I,suitable substituents in this case can be, if not stated otherwise, e.g.C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, amino, C₁ -C₄ -mono-ordialkylamino, nitro, formyl, cyano, carboxyl or hydroxysulfonyl. As arule, they contain 1 to 3 substituents.

The radicals R¹, R² and R³ are e.g. methyl, ethyl, propyl, isopropyl,butyl, isobutyl or sec-butyl.

The radicals R⁴ are e.g. methylsulfonyl, ethylsulfonyl, propylsulfonyl,isopropylsulfonyl or butylsulfonyl.

The radicals A are e.g. --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅--, --(CH₂)₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --CH(CH₃)--CH₂ --,--CH(CH₃)--CH(CH₃)--, --(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₂ --NH--(CH₂)₂ --,--(CH₂)₂ --N(CH₃)--(CH₂)₂ --, --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ -- or--(CH₂)₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --.

Y in formula I is, inter alia, a group which can be removed underalkaline reaction conditions. Such groups are e.g. chlorine, OSO₃ H,SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, unsubstituted orsubstituted phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄-dialkylamino, ##STR5## Q¹, Q² and Q³ being identical or different andindependently of one another in each case having the meaning of C₁ -C₄-alkyl or benzyl and An.sup.⊖ in each case having the meaning of ananion. (Suitable anions are e.g. fluoride, chloride, bromide, iodide,mono-, di- or trichloroacetates, methanesulfonates, benzenesulfonates or2- or 4-toluenesulfonate.)

Preferred Y groups are C₁ -C₄ -alkanoyloxy, in particular acetoxy.

Suitable bridge members L comply e.g. with the formula ##STR6## L¹ beingC₂ -C₈ -alkylene, Q⁴ being hydrogen or hydroxysulfonyl and Q⁵ beinghydrogen or C₁ -C₄ -alkyl.

Individual bridge members are e.g. radicals of the formula ##STR7##

The radicals D are e.g. 2,4-dihydroxysulfonylphenyl,2,5-dihydroxysulfonylphenyl, 2,5-dihydroxysulfonyl-4-methylphenyl,2,5-dihydroxysulfonyl-6-chlorophenyl,3,6,8-trihydroxysulfonylnaphth-2-yl,4,6,8-trihydroxysulfonylnaphth-2-yl, 1,5-dihydroxysulfonylnapth-2-yl or1,6-dihydroxysulfonylnaphth-2-yl.

Preferred compounds of the formula I are those where

R¹, R² and R³ are in each case hydrogen,

R⁴ is fluorine or chlorine,

A is C₂ -C₄ -alkylene, which may be interrupted by an ether oxygen, and

D is phenyl or naphthyl, these radicals being mono- to trisubstituted byhydroxysulfonyl.

Particularly preferred compounds of the formula I are those where

D is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl.

Particularly preferred compounds of the formula I are furthermore thosewhere, if n is 1, L is a radical of the formula ##STR8## where Q⁴ and Q⁵in each case have the abovementioned meanings.

The novel compounds of the formula I are advantageously obtained if e.g.an amine of the formula III

    D--NH.sub.2                                                (III),

where D has the abovementioned meanings, is diazotized and coupled in aknown manner with a phenylenediamine of the formula IV ##STR9## whereR¹, R², R³, A and Y in each case have the abovementioned meanings.

The resulting azo compound of the formula V ##STR10## where D, R¹, R²,R³, A and Y in each case have the abovementioned meanings, can bereacted with trihalotriazine in a known manner. The reaction can becarried out in this case in a one-pot process or with isolation of theintermediates.

In order to obtain those compounds of the formula I in which n is zero,the reaction product can be reacted with further azo compound V.

In order to obtain those compounds of the formula I in which n is one,the product formed in the reaction with trihalotriazine can be reactedwith a diamine of the formula VI

    H.sub.2 N--L--NH.sub.2                                     (VI),

where L has the abovementioned meaning.

The phenylenediamines of the formula IV can be obtained by the methoddescribed in the earlier European Patent Application No. 93 115 520.4.

The novel compounds of the formula I are useful intermediates forpreparing reactive dyes.

Accordingly, the present invention furthermore relates to a process forpreparing reactive dyes of the formula II ##STR11## where n is 0or 1 l

R¹, R² and R³ are identical or different and independently of oneanother are in each case hydrogen, C₁ -C₄ -alkyl or phenyl,

R⁴ is fluorine, chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonylor a radical of the formula ##STR12## L is a bridge member, A is C₂ -C₈-alkylene which may be interrupted by 1 to 3 ether oxygen atoms, iminogroups or C₁ -C₄ -alkylimino groups,

Y is vinyl or a radical of the formula--CH₂ --CH₂ --Q, Q being a groupwhich can be removed under alkaline reaction conditions, and

D is phenyl or naphthyl, it being possible for these radicals to bemono- or polysubstituted by hydroxysulfonyl, carboxyl, C₁ -C₄-alkoxycarbonyl, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro orvinylsulfonyl,

which comprises treating compounds of the formula I ##STR13## where n,R¹, R², R³, R⁴, L, A, Y and D in each case have the abovementionedmeanings, in aqueous medium with an oxidant, if appropriate in thepresence of catalysts, at from 0° to 110° C.

As far as the exemplary explanation of said radicals is concerned,reference may be made to the embodiments above.

Suitable oxidants are organic or inorganic oxidants, such as hydrogenperoxide, hydrogen peroxide-releasing compounds, organic hydroperoxides,percarboxylic acids, peroxomonosulfuric acid or its salts, in particularits alkali metal salts, peroxodisulfuric acid or its salts, inparticular its alkali metal salts, alkali metal hypohalites, alkalimetal permanganates, chromic acid or its salts, in particular its alkalimetal salts, or nitric acid.

Suitable hydrogen peroxide-releasing compounds can be e.g. alkali metalperborates or percarbonates.

Suitable organic hydroperoxides are e.g. cumene hydroperoxide or alkylhydroperoxides, in this case in particular tert-butyl hydroperoxide.

Suitable percarboxylic acids are e.g. peracetic acid, m-chloroperbenzoicacid, magnesium bis(monoperoxyphthalate)hexahydrate or1,12-dodecanediperacid.

The use of hydrogen peroxide as an oxidant is preferred.

As a rule, hydrogen peroxide is used in the process according to theinvention as a 3 to 80% strength by weight aqueous hydrogen peroxidesolution, 2-10 mol, preferably 2-4 mol, of aqueous hydrogen peroxide ingeneral being used per mole of compound of the formula I.

Based on one part by weight of the compound of the formula I, a further1 to 10 parts by weight of water are customarily additionally used as areaction medium.

The process according to the invention can be carried out in thepresence of catalysts. Suitable catalysts are e.g. alkali metaltungstates, alkali metal molybdates or alkali metal vanadates, such aslithium tungstate, molybdate or vanadate, sodium tungstate, molybdate orvanadate or potassium tungstate, molybdate or vanadate.

As a rule, 0.001-0.1 part by weight of catalyst are used per part byweight of compound of the formula I.

The carrying out of the novel process in the presence of a catalyst ispreferred, alkali metal tungstates, in particular sodium tungstate,being particularly emphasized as catalysts.

According to the invention, the oxidation of the thioether takes placeat from 0° to 110° C., preferably 20° to 80° C. Customarily, oxidationis carried out under atmospheric pressure.

It is recommended to carry out the oxidation at a pH from 0 to 8,preferably 4 to 7.

The novel process, which can be carried out either continuously orbatchwise, is expediently carried out by introducing the compound of theformula I together with water and, if desired, catalysts and setting theabovementioned pH range, if appropriate with the addition of base, e.g.sodium hydrogencarbonate. The oxidant is then added at theabovementioned temperature. In general, the mixture is then stirred atfrom 20° to 80° C. for 0.5-5 hours. The resulting reaction mixture isthen filtered and the filtrate containing the reactive dye II can befreed of solvent and dried.

The novel process can be carried out in a simple manner and yields thereactive dyes of the formula II in high yield and purity.

As already mentioned above, the reactive dyes of the formula II areuseful products for dyeing or printing organic substrates containinghydroxyl groups or nitrogen atoms.

The following examples are intended to illustrate the invention ingreater detail:

EXAMPLE 1

a) 462 g of a water-moist suction filter material (dry content: 70% byweight) of nitrophenylurea were treated with 700 g of xylene (isomermixture) and 242 g of 2-aminoethyl-2'-hydroxyethyl sulfide and themixture was heated to boiling. The xylene-water azeotrope boiling at 95°C. was removed by distillation and the reaction mixture was then heatedto 140° C. to remove the residual xylene. After completion of thereaction (TLC checking), the mixture was cooled to 50° C. and 1 liter ofwater was added. The reaction mixture was adjusted to a pH of 11 using20% strength by weight sodium hydroxide solution. The aqueous phase wasthen separated off and the water remaining in the organic phase wasremoved by azeotropic distillation. 6 g of 1-methylimidazole were addedafter cooling to 65° C. 277 g of acetic anhydride were added dropwise atthis temperature. After cooling to 20° C., the resulting precipitate wasfiltered off with suction. 555 g of the compound of the formula##STR14## were obtained. The following nitrophenylureas can be preparedin a similar manner: ##STR15##

b) 565 g of the compound Z1 were suspended in 1800 ml of isobutanol. 130g of Raney nickel were added to this mixture. It was then hydrogenatedat 55°-60° C. in the course of 15 h by passing in hydrogen gas. Aftercompletion of the reaction (TLC checking), the catalyst was filteredoff. The filtrate was concentrated under reduced pressure. The oil whichreined crystallized after a short time. The crystals were filtered offwith suction. 495 g of the compound of the formula ##STR16## wereobtained.

The following amino compounds can be prepared in a similar manner:##STR17## c) 101 g (0.4 mol) of aniline-2,4-disulfonic acid werediazotized in 400 ml of water containing hydrochloric acid and added toa suspension of 119 g (0.4 mol) of the compound Z4 in 500 ml of water.The coupling reaction was carried out at 0°-5° C. and a pH of 3 byaddition of 2N potassium hydrogen carbonate solution.

d) The reaction solution described above was halved and the first halfwas condensed with 40.6 g (0.22 mol) of cyanuric chloride at 0°-5° C.and a pH of 5.5. The solution was then subjected to clarifyingfiltration and reacted with the second half of the coupling solution at40°-50° C. and a pH of 5.5. After salting out, 204 g of the compound##STR18## were obtained

In order to obtain the compound described in d), the following procedurecan also be used.

e) 254 g (1 mol) of aniline-2,4-disulfonic acid were diazotized with 320ml of 23% strength by weight aqueous sodium nitrite solution in 1,000 gof ice/water mixture at 0°-5° C. 297 g (1.0 mol) of the compound Z4,suspended in 500 g of water, were then added and the coupling reactionwas carried out at a pH of 3 with the aid of aqueous 1N sodiumhydrogencarbonate solution. The resulting coupling solution was thentreated with a mixture of 92 g (0.5 mol) of cyanuric chloride and 250 gof ice water. The 1st condensation step was then carried out at 0°-5° C.and a pH of 5.5, which was set by addition of sodium hydrogencarbonatesolution. After 1 hour, the reaction mixture was heated to 40°-45° C.for the 2nd condensation step and a pH of 5.5 was maintained by means ofsodium hydrogencarbonate solution. The resulting compound corresponds,as the free acid, to the compound described in Example 1d) and wasisolated by salting out.

The compounds of the formula ##STR19## listed in Table 1 can be obtainedin a similar manner.

                  TABLE 1                                                         ______________________________________                                        Ex. No. D                     E       m                                       ______________________________________                                         2                                                                                     ##STR20##            H       2                                        3                                                                                     ##STR21##            H       3                                        4                                                                                     ##STR22##            CH.sub.3                                                                              2                                        5                                                                                     ##STR23##            H       3                                        6                                                                                     ##STR24##            CH.sub.3                                                                              2                                        7                                                                                     ##STR25##            H       2                                        8                                                                                     ##STR26##            H       3                                        9                                                                                     ##STR27##            CH.sub.3                                                                              2                                       10                                                                                     ##STR28##            H       2                                       11                                                                                     ##STR29##            H       3                                       12                                                                                     ##STR30##            CH.sub.3                                                                              2                                       13                                                                                     ##STR31##            CH.sub.3                                                                              2                                       14                                                                                     ##STR32##            H       3                                       15                                                                                     ##STR33##            CH.sub.3                                                                              2                                       16                                                                                     ##STR34##            H       2                                       17                                                                                     ##STR35##            H       3                                       18                                                                                     ##STR36##            CH.sub.3                                                                              2                                       19                                                                                     ##STR37##            H       2                                       20                                                                                     ##STR38##            H       3                                       21                                                                                     ##STR39##            CH.sub.3                                                                              2                                       ______________________________________                                    

EXAMPLE 22

0.4 mol of the coupling solution described in Example 1c) was condensedwith 81.2 g (0.44 mol) of cyanuric chloride at 0°-5° C. and a pH of 5.5.The reaction solution was then subjected to clarifying filtration andtreated with 21.6 g (0.2 mol) of para-phenylenediamine. To complete thereaction, the reaction mixture was heated to 40°-50° C. and a pH of 5.5was maintained by addition of 2N sodium hydroxide solution. The compoundcould be isolated by spray drying and corresponds to the formula##STR40##

The compounds of the formula ##STR41## listed in Table 2 can be obtainedin a similar manner.

                  TABLE 2                                                         ______________________________________                                        Ex. No. L                                                                     ______________________________________                                        23                                                                                     ##STR42##                                                            24      HNC.sub.2 H.sub.4NH                                                   25      HNC.sub.2 H.sub.4NH                                                   26                                                                                     ##STR43##                                                            27                                                                                     ##STR44##                                                            ______________________________________                                    

EXAMPLE 28

0.4 mol of the coupling solution described in Example 1c) was reactedwith 81.2 g (0.44 mol) of cyanuric chloride at 0° to 5° C. and a pH of5.5. The reaction solution was then subjected to clarifying filtrationand treated with 37.6 g (0.2 mol) of 2,4-diaminobenzenesulfonic acid. Tocomplete the reaction, the reaction mixture was heated to 40°-50° C. anda pH of 5.5 was maintained using 2N sodium hydroxide solution. Theresulting compound was isolated by evaporating the reaction solution. Itcorresponds to the formula ##STR45##

The compounds of the formula ##STR46## listed in Table 3 can be obtainedin a similar manner.

                  TABLE 3                                                         ______________________________________                                        Ex. No. L                                                                     ______________________________________                                        29                                                                                     ##STR47##                                                            30                                                                                     ##STR48##                                                            31                                                                                     ##STR49##                                                            32                                                                                     ##STR50##                                                            33                                                                                     ##STR51##                                                            ______________________________________                                    

EXAMPLE 34

100 g of the compound obtained according to Example 1d) were added to250 ml of water. A pH of 6 was set using sodium hydrogencarbonate. 0.5 gof sodium tungstate was then added and 20 g of 30% strength by weightaqueous hydrogen peroxide solution were added dropwise. The resultingreaction mixture was stirred at 60° C. for 2 hours and filtered. Thefiltrate was concentrated under reduced pressure and the residue wasdried. 98 g of the reactive dye of the formula ##STR52## were obtained.

It dyes cotton in a yellow shade having a very good lightfastness andvery good wetfastnesses.

The abovementioned compounds can be oxidized to the correspondingreactive dyes in a similar manner.

We claim:
 1. A compound of the formula I ##STR53## where n is 0 or 1R¹, R² and R³ are identical or different and independently of one another are in each case hydrogen, C₁ -C₄ -alkyl or phenyl, R⁴ is fluorine, chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl or a radical of the formula ##STR54## L is a bridge member, A is C₂ -C₈ -alkylene which my be interrupted by 1 to 3 ether oxygen atoms, imino groups or C₁ -C₄ -alkylimino groups, Y is vinyl or a radical of the formula --CH₂ --CH₂ --Q, Q being a group which can be removed under alkaline reaction conditions, and D is phenyl or naphthyl, it being possible for these radicals to be mono- or polysubstituted by hydroxysulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro or vinylsulfonyl.
 2. A compound as claimed in claim 1, whereinR¹, R² and R³ are in each case hydrogen, R⁴ is fluorine or chlorine, A is C₂ -C₄ -alkylene which may be interrupted by an ether oxygen, and D is phenyl or naphthyl, these radicals being mono- to trisubstituted by hydroxysulfonyl. 